A novel and environmentally friendly strategy has been developed for the efficient electrochemical synthesis of β-keto sulfones. This method enables the synthesis of β-keto sulfones by reacting easily available sulfonylhydrazide with enol acetate under mild conditions, especially without the need for transition metal catalysts or oxidants, which can achieve high yields. The scope of this reaction was systematically explored with various sulfonyl hydrazides and enol acetates. The scale-up synthesis of β-keto sulfones was successfully accomplished using an electrochemical flow cell, demonstrating the industrial applicability of this approach. Moreover, the underlying reaction mechanism was further investigated through free radical scavenging experiments and cyclic voltammetry studies.